WO2006062037A1

WO2006062037A1 - Composition for metal surface treatment, treating liquid for surface treatment, method of surface treatment, and surface-treated metallic material

Info

Publication number: WO2006062037A1
Application number: PCT/JP2005/022176
Authority: WO
Inventors: Masayuki Yoshida; Katsuyuki Kawakami
Original assignee: Henkel Kommanditgesellschaft Auf Aktien; Nihon Parkerizing Co., Ltd.
Priority date: 2004-12-08
Filing date: 2005-12-02
Publication date: 2006-06-15
Also published as: CA2591214A1; EP2302097A4; AU2005312758A1; JP4242827B2; MX2007006729A; PL2302097T3; EP2302097A1; BRPI0518423A2; EP2302097B1; JP2006161117A; US20070272900A1; CN101076615A; CN101076615B; ES2529318T3; RU2395622C2; BRPI0518423B1; CA2591214C; RU2007125572A; AU2005312758B2

Abstract

A surface-treating composition which is a treating liquid containing no ingredients harmful to the environment; such a treating liquid has been difficult to obtain with any conventional technique. The composition enables a coating film having excellent corrosion resistance after coating to be deposited through surface treatment on a surface of a metallic material, e.g., an iron-based metallic material. The composition, which is for the surface treatment of a metal comprising iron and/or zinc, comprises the following ingredients (A), (B), and (C): (A) a compound containing at least one element selected from the group consisting of titanium, zirconium, hafnium, and silicon; (B) a compound containing yttrium and/or a lanthanide element; and (C) nitric acid and/or a nitric acid compound. In the composition, the ratio of the total mass concentration B of the yttrium and/or lanthanide element in the ingredient (B) to the total mass concentration A of the element(s) in the ingredient (A), K1=B/A, is 0.05≤K1≤50 and the ratio of the total mass concentration C of nitrogen atoms in the ingredient (C) in terms of NO3 concentration to the total mass concentration A, K2=C/A, is 0.01≤K2≤200.

Description

Specification

Metal surface treatment composition, surface treatment liquid, surface treatment method, and surface-treated metal material

Technical field

[0001] The present invention relates to a surface treatment composition capable of depositing a surface treatment film excellent in corrosion resistance after coating or bare corrosion resistance on the surface of a metal material represented by building materials and home appliances, etc. The present invention relates to a treatment liquid for treatment, a surface treatment method, and a metal material obtained by the treatment method.

Background art

[0002] As a method for depositing a surface treatment film having excellent corrosion resistance after coating on a metal surface, a zinc phosphate treatment method and a chromate treatment method are currently generally used. The zinc phosphate treatment method can deposit a film having excellent corrosion resistance on steel such as hot-rolled steel sheet or cold-rolled steel sheet or zinc-plated steel sheet.

[0003] However, when zinc phosphate treatment is performed, the generation of sludge as a by-product of the reaction is inevitable. In addition, the ability to ensure sufficient post-painting performance by applying chromate treatment. In view of the recent environmental regulations, chromate treatment containing harmful hexavalent chromium in the treatment liquid tends to be avoided. It is in.

[0004] Therefore, as a recent technology, a technology has been developed in which the surface of the material is coated with a metal thin film such as zirconium to provide corrosion resistance, and the processing liquid does not contain harmful components and suppresses the generation of sludge. Has been. As these surface treatment methods, the following methods have been proposed.

[0005] For example, Patent Document 1 describes a compound containing a nitrogen atom having a lone electron pair, and a non-chromium coating agent for a metal surface containing the compound and a zirconium compound. The purpose of this method is to obtain a surface-treated film excellent in corrosion resistance and adhesion after coating without applying hexavalent chromium, which is a harmful component, by applying the composition. .

[0006] However, the target metal material is limited to the aluminum alloy, and Since the surface treatment film is formed by drying the cloth, it is difficult to apply it to complicated structures.

[0007] Therefore, as a method for depositing a surface treatment film having excellent adhesion and corrosion resistance after coating by a chemical conversion reaction, Patent Document 2 discloses a surface treatment agent using cerium, zirconium, phosphoric acid, a fluorinated compound, And the treatment bath is described.

However, as with the invention described in Patent Document 1, this method is also limited to the target metal material being aluminum or an aluminum alloy that is excellent in the corrosion resistance of the material itself. It was impossible to deposit a surface treatment film on the surface of a zinc-based material or a zinc-based material.

[0009] Patent Document 3 describes a surface treatment composition comprising a metal acetylacetonate and a water-soluble inorganic titanium compound or a water-soluble inorganic zirconium compound, and is excellent in corrosion resistance and adhesion after coating. A method for depositing a surface treatment film is described. By using this method, the metal materials applied were expanded to magnesium, magnesium alloys, zinc, and zinc-plated alloys in addition to aluminum alloys.

However, with this method, it has been impossible to deposit a surface treatment film on the surface of an iron-based metal material such as a hot-rolled steel sheet or a cold-rolled steel sheet.

Furthermore, Patent Document 4 describes a metal surface treatment method using a chromium-free coating-type acidic composition. In the metal surface treatment method, an aqueous solution of a component capable of forming a film having excellent corrosion resistance is applied to the metal surface, and then the film is fixed by baking and drying without performing a water washing step. Therefore, since no chemical reaction is involved in the formation of the coating, it is possible to perform coating treatment on metal surfaces such as hot-rolled steel sheets, cold-rolled steel sheets, zinc-plated steel sheets, and aluminum alloys.

However, as in the invention described in Patent Document 1, since a film is formed by coating and drying, it is difficult to perform a uniform film treatment on a complicated structure.

[0013] Furthermore, Patent Document 5 discloses a metal chemical conversion treatment method containing zirconium ions, Z or titanium ions, and fluorine ions in a treatment bath. By using this method, the target metal materials can be applied to iron, aluminum and zinc. However, there is a constraint that the iron ion concentration in the chemical conversion treatment agent must be controlled by the oxidizing agent during the treatment.

[0015] Therefore, the conventional technology does not contain components harmful to the environment! /, And is excellent in corrosion resistance and adhesion for processing liquids and metal materials such as iron-based metal materials and zinc-based metal materials. In addition, it was impossible to perform surface treatment with excellent operability.

Patent Document 1: Japanese Patent Laid-Open No. 2000-204485

Patent Document 2: JP-A-2-25579

Patent Document 3: Japanese Unexamined Patent Publication No. 2000-199077

Patent Document 4: JP-A-5-195244

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-43913

Disclosure of the invention

Problems to be solved by the invention

[0016] The present invention is a treatment liquid that does not contain a component harmful to the environment, which has been difficult with the prior art, and is a hot-rolled steel sheet such as a hot-rolled steel sheet and a cold-rolled steel sheet used in home appliances and the like. Surface treatment composition that makes it possible to deposit a surface-treated film with excellent corrosion resistance after coating or bare corrosion resistance on the surface of metallic materials such as metallic materials and zinc-based metallic materials such as galvanized steel sheets. The object is to provide a product, a surface treatment liquid, a surface treatment method, and a surface-treated metal material.

Means for solving the problem

[0017] As a result of intensive investigations on means for solving the above problems, the present inventors have found a surface treatment composition, a surface treatment solution, a surface treatment method, and a surface treatment metal material that are not present in the prior art. It came to be completed.

[0018] Such problems are achieved by the present inventions (1) to (17) below.

[0019] (1) The following components (A), (B), and (C):

(A) Group force consisting of Ti, Zr, Hf, and Si forces A compound containing at least one element selected

(B) Compounds containing Y and Z or lanthanoid elements

(C) Nitric acid and Z or nitrate compounds

In the component (B) with respect to the total mass concentration A of the elements in the component (A) Kl = BZA, which is the ratio of the total mass concentration B of Y and Z or lanthanoid elements, is 0.05≤K1≤50, and NO conversion of nitrogen atoms in the component (C) with respect to the total mass concentration Α Is the ratio of the total mass concentration C K2 = CZA force 0.01≤K2≤200,

Three

A composition for surface treatment of a metal containing iron and iron or zinc.

[0020] (2) Further, the following component (D):

(D) At least one fluorine-containing compound

The composition for surface treatment according to the above (1), comprising:

[0021] (3) The following component (Α), component (Β), and component (C):

(B) Compounds containing Y and Z or lanthanoid elements

(C) Nitric acid and Z or nitrate compounds

Kl = BZA, which is the ratio of the total mass concentration B of the Y and Z or lanthanoid elements in the component (B) to the total mass concentration A of the elements in the component (A) is 0.05. ≤K1≤50, which is the ratio of the total mass concentration C in terms of NO of the nitrogen atom in the component (C) to the total mass concentration K K2 = CZA force 0.01≤K2≤200,

Three

A treatment liquid for surface treatment of a metal containing iron and Z or zinc, wherein the total mass concentration Α is 10 ppm≤A≤10000 ppm.

[0022] (4) Further, the following component (D):

(D) At least one fluorine-containing compound

The surface treatment solution according to (3) above, wherein the free fluorine ion concentration D is 0.001 ppm≤D≤300 ppm.

[0023] (5) The treatment liquid for surface treatment according to (3) or (4), wherein the pH is 6.0 or less.

[0024] (6) Further, HC1, HSO, HCIO, HBrO, HNO, HMnO, HVO, H2O, HWO, H

2 4 3 3 2 4 3 2 2 2 4 2

At least one selected from the group consisting of MoO and salts thereof contains 10 to 20000 ppm.

Four

The treatment liquid for surface treatment according to any one of (3) to (5) above.

[7] (7) Further, from ethylenediamine tetraacetic acid, darconic acid, heptogluconic acid, glycolic acid, succinic acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid, and salts thereof Group power of at least one selected from 1 to: LOOOOppm included The treatment liquid for surface treatment according to any one of (3) to (6) above.

[0026] (8) The treatment liquid for surface treatment according to any one of (3) to (7), further comprising a water-soluble polymer compound and Z or a water-dispersible polymer compound.

[0027] (9) The above (3) to (8) further comprising at least one selected from the group force consisting of a non-ionic surfactant, a ionic surfactant and a cationic surfactant. ) The surface treatment treatment liquid according to any one of the above.

[0028] (10) Iron and Z or a metal having a treatment liquid contact step in which the surface treatment liquid according to any one of (3) to (8) is brought into contact with a metal material containing iron and Z or zinc. Surface treatment method for metals containing zinc.

[0029] (11) A treatment liquid contact in which the metal composition containing iron and Z or zinc is contacted with the treatment liquid for surface treatment according to (9) above, and the degreasing treatment and film forming treatment of the metal material are performed simultaneously. A method for treating a surface of a metal containing iron and Z or zinc, comprising a step.

[0030] (12) The surface treatment method according to (10) or (11) above, wherein the metal material containing iron and Z or zinc is a metal material cleaned by a degreasing treatment.

[0031] (13) The surface treatment according to any one of (10) to (12), wherein in the treatment liquid contact step, electrolytic treatment is performed using the metal material containing iron and Z or zinc as a cathode. Method.

(14) Further, after the treatment liquid contact step,

Contacting the metal material containing iron and Z or zinc with an aqueous solution containing at least one selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium. The surface treatment method according to any one of (10) to (13) above.

(15) Furthermore, after the treatment liquid contact step,

The above (10) to (13), comprising the step of bringing the metal material containing iron and Z or zinc into contact with an aqueous solution containing a water-soluble polymer compound and Z or a water-dispersible polymer compound. The surface treatment method as described.

(16) The surface of the metal material containing iron contains the element of the component (A) formed by the surface treatment method according to any one of (10) to (15), and A metal material containing iron having a surface-treated film layer having an adhesion amount in terms of element of not less than 0 mg / m ² .

[0035] (17) The surface treatment according to any one of (10) to (15) above is performed on the surface of the metal material containing zinc. A metal material containing zinc, comprising a surface treatment film layer containing the element of the component (A) and having an adhesion amount of the element conversion of 15 mg / m ² or more, formed by a method. effect

The metal surface treatment composition, surface treatment solution, surface treatment method, and surface treatment metal material of the present invention are treatments that do not contain components harmful to the environment, which are difficult in the prior art. This is an epoch-making technology that allows a surface treatment film with excellent corrosion resistance after coating to be deposited on the surface of a metal material in a bath.

BEST MODE FOR CARRYING OUT THE INVENTION

[0037] Hereinafter, the metal surface treatment composition of the present invention (hereinafter also simply referred to as "the composition of the present invention"), the metal surface treatment solution of the present invention (hereinafter simply referred to as "the treatment liquid of the present invention"). The metal surface treatment method of the present invention (hereinafter also simply referred to as “the treatment method of the present invention”) and the metal material containing iron and Z or zinc of the present invention (hereinafter also simply referred to as “the metal material of the present invention”). ) Will be explained in detail. First, the composition and the treatment liquid of the present invention will be described.

[0038] At the time of use, the composition of the present invention is diluted with water or dissolved in water to obtain the treatment liquid of the present invention.

The object of the surface treatment with the treatment liquid of the present invention is an iron-based metal material or a zinc-based metal material.

The iron-based metal material is not particularly limited as long as it contains iron, and examples thereof include steel plates such as cold rolled steel plates and hot rolled steel plates, pig iron, and sintered materials.

The zinc-based metal material is not particularly limited as long as it contains zinc. For example, a zinc die-cast material or a zinc-containing material is shown. Furthermore, a zinc-containing metal plating is zinc or an alloy of zinc and other metals such as nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead, and antimony, and unavoidable. This is due to impurities, and there are no restrictions on the method of plating, for example, electric plating, melting plating, or vapor deposition.

[0039] In the present invention, surface treatment is performed on the surface of such a metal material. In addition, the metal materials to be treated can be surface-treated alone or at least two kinds at the same time. Where two or more gold When processing metal materials at the same time, if at least one of the metal materials is iron or zinc-based metal material, other metal materials such as aluminum, magnesium, nickel and their alloys It does not matter. Further, the dissimilar metals may not be in contact with each other, or the dissimilar metals may be in contact with each other by a joining method such as welding, adhesion, or riveting.

The operation of the present invention will be described in detail below.

[0040] The composition of the present invention contains the following component (A), component (B), and component (C).

Component (A) is a compound containing at least one element selected from the group force of Ti, Zr, Hf, and Si force. Examples of such compounds include TiCl, Ti (SO), TiOSO, Ti (NO)

4 4 2 4 3 4

, TiO (NO), Ti (OH), TiO OC O, H TiF, H TiF salt, TiO, TiO, Ti O, TiF, Zr

3 2 4 2 2 4 2 6 2 6 2 2 3 4

CI, ZrOCl, Zr (OH) CI, Zr (OH) Cl, Zr (SO), ZrOSO, Zr (NO), ZrO (NO), Zr (0

4 2 2 2 3 4 2 4 3 4 3 2

H), H ZrF, H ZrF salt, H (Zr (CO) (OH)), H (Zr (CO) (OH)) salt, H Zr (OH) (S

4 2 6 2 6 2 3 2 2 2 3 2 2 2 2

O), H Zr (OH) (SO) salt, ZrO, ZrOBr, ZrF, HfCl, HKSO), H HIF, H HIF

4 2 2 2 4 2 2 2 4 4 4 2 2 6 2 6 salt, salt, HIF, H SiF, H SiF salt, and Al 2 O 3 (SiO 2). These are two or more

2 4 2 6 2 6 2 3 2 3

The above may be used together.

[0041] The component) is a compound containing Y and Z or a lanthanoid element. In other words, it is a compound containing at least one selected from the group forces such as Y, La L Ce ゝ Pr ゝ Nd, Pm ゝ Sm ゝ Eu ゝ Gd, Tb ゝ Dy ゝ Ho, Er ゝ Tm ゝ Yb ゝ and Lu force. is there. Such compounds include oxides, sulfates, nitrates, and salts of these elements. Specifically, for example, salt yttrium, lanthanum chloride, salt cerium, salt 匕 praseodymium, salt 匕 neodymium, salt 匕 promethium, salt 匕 samarium, salt 匕 samarium, salt 匕Gadolinium, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, yttrium sulfate, lanthanum sulfate, cerium sulfate, prasedium sulfate, neodymium sulfate, promethium sulfate, samarium sulfate, sulfuric acid Pitium, gadolinium sulfate, terbium sulfate, dysprosium sulfate, holmium sulfate, erbium sulfate, thulium sulfate, ytterbium sulfate, lutetium sulfate, yttrium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethy nitrate Beam, samarium nitrate, nitric acid Yu opening Piumu, nitric acid gadolinium, terbium nitrate, dysprosium nitrate, nitric acid Horumiu , Erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, yttrium oxide, acid lanthanum, acid cerium, acid praseodymium, acid neodymium, promethium oxide, acid samarium, acid , Ytterbium oxide, ytterbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and yttrium oxide. Two or more of these may be used in combination.

[0042] Component (C) is nitric acid and Z or a nitric acid compound. Examples of such include nitric acid and metal nitrates. Examples of the metal nitrate include iron nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, silver nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, and calcium nitrate. Two or more of these may be used in combination.

[0043] The composition of the present invention is used by diluting with water or dissolving in water for the surface treatment of metal. That is, a metal surface treatment solution is prepared and used. To prepare the metal surface treatment solution, water is added to the surface treatment composition, and the total mass concentration A of the elements (Ti, Zr, Hf, and Si) in the component (A) is from lOppm. Try to be in the lOOOOppm range.

[0044] The "total mass concentration A of the elements in the component (A)" means "the elements in the component (A) in the composition of the present invention (in some cases, a treatment liquid)". Concentration ". The same applies to “total mass concentration B” and “total mass concentration C”.

[0045] The present invention provides the surface treatment composition and the surface treatment solution and the Y and Z or lanthanoid in the component (B) relative to the total mass concentration A of the element in the component (A). K1 = BZA force 0.05 ≤ K1 ≤ 50, and the total mass concentration C of nitrogen atoms in the component (C) with respect to the total mass concentration 換算

Three

The ratio of K2 = C / A is 0.01≤K2≤200.

[0046] Here, component (i) is a substance having excellent acid resistance and alkali resistance! And is a main component of the surface treatment film of the present invention.

In addition, component) has an effect of promoting film deposition of component (ii). Furthermore, the component) can also be contained in the surface treatment film, which can be expected to improve the corrosion resistance after coating and the bare corrosion resistance. In addition, component (C) has a function of maintaining the stability of the treatment liquid by increasing the solubility of component (A) and component (B) in the treatment liquid for surface treatment. Furthermore, component (C) has the effect of assisting the film deposition of component (A), as is the case with component (B).

[0047] Here, if Kl = BZA is too small, the proportion of component (B) is small, and therefore the effect of promoting film deposition of component (A) by component (B) cannot be expected. Therefore, compared with the case where K1, which is the ratio of the total mass concentration of component (A) and component (B), is 0.05 ≤ K1 ≤ 50, the coating amount of component (Α) decreases, and the metal material to be treated Corrosion resistance may decrease.

Further, if K1 is too large, the reaction starting point of the component (v) on the surface of the metal material to be treated is reduced, and although it has an accelerating effect due to the component), it is a main component of the film and imparts corrosion resistance to the film. Because the amount of coating of the component (皮膜) decreases, it may not only exhibit excellent corrosion resistance but may also adversely affect adhesion.

[0048] Further, even if K2 = CZA is too small, the corrosion resistance of the metal material to be treated can be obtained, but the stability of the treatment liquid of the treatment liquid for surface treatment may be impaired. Operational problems may occur. Furthermore, since the ratio of component (C) in the treatment solution is low, the auxiliary effect of component (A) on film deposition of component (A) cannot be expected.

Further, in order to maintain the stability of the processing solution of the present invention, it is sufficient that K2 = CZA is within the range of 0.01 ≤ K2 ≤ 200. Corrosion resistance is not improved even if Κ2 is too large. It is just disadvantageous.

[0049] The total mass concentration 濃度 of the component (濃度) used in the treatment liquid of the present invention is preferably adjusted to lOppm force lOOOOppm, more preferably from 50ppm to 5000ppm. If the total mass concentration A is too small, even if the Kl and っても 2 are within the specified range, the concentration of the main component of the film is low, so that a sufficient amount of adhesion can be obtained in a practical treatment time to obtain corrosion resistance. It becomes difficult to obtain. On the other hand, if the total mass concentration 付着 is too large, a sufficient amount of adhesion can be obtained, but the effect of further improving the corrosion resistance is only economically disadvantageous.

[0050] The composition and the treatment liquid of the present invention preferably further contain at least one fluorine-containing compound as component (D). For example, hydrofluoric acid, H TiF, H TiF salt,

2 6 2 6

TiF, H ZrF, H ZrF salt, ZrF, H H1F, H H1F salt, H1F, H SiF, HBF, HBF Salt, NaHF, KHF, NH HF, NaF, KF, and NH F. Also these

2 2 4 2 4

Two or more fluorine-containing compounds may be used in combination.

[0051] When component (D) is added to the treatment liquid of the present invention, at least one fluorine-containing compound of component (D) is adjusted so that the free fluorine ion concentration D is from 0.001 ppm to 300 ppm. More preferably, it is preferable to adjust it to be from 0.1 ppm to 10 ppm. The free fluorine ion concentration D mentioned here indicates the fluorine ion concentration measured using a commercially available ion electrode. If the free fluorine ion concentration D is too large, the etching reaction on the surface of the material by HF becomes excessive, and it tends to be difficult to deposit a coating amount sufficient to obtain corrosion resistance on the surface of the metal material to be treated. In addition, the corrosion resistance of the metal material to be treated can be obtained even if the free fluorine ion concentration D due to the fluorine-containing compound of component (D) is too small, but the stability of the treatment liquid of the surface treatment liquid may be impaired. There is a possibility of hindering continuous operation.

[0052] In addition, the treatment liquid of the present invention preferably deposits a film by a chemical conversion reaction involving etching of the material metal. Therefore, it is preferable to use at pH 6.0 or lower, which is a pH range where etching reaction can generally occur, more preferably at pH 5.0 or lower, and even more preferably at pH 4.0 or lower. Is preferred.

[0053] Here, when it is necessary to adjust the pH of the treatment liquid of the present invention, there is no particular limitation on the agent to be used, and any of them may be used. For example, acids such as hydrochloric acid, sulfuric acid, boric acid, and organic acids, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, alkali metal salts, ammonia, ammonia Salts and amines such as amines are available.

[0054] In the treatment liquid of the present invention, metals contained in the material eluted by the etching reaction of the material, metals and compounds contained in tap water, and industrial water may be mixed into the treatment liquid. . This is because component (B) accelerates film deposition of component (A), and film deposition of component (A) is not affected by other metal elements or compounds.

[0055] In addition, an anion component is preferably added to the treatment liquid of the present invention in order to further accelerate the film formation reaction. For example, HC1, HSO, HCIO, HBrO, HNO, HMnO, HVO, HO, HW can be used as the ion component that can be used in the surface treatment solution of the present invention. O, H MoO and their salts. To the concentration of these key components

4 2 4

Although there is no particular regulation, the effect is sufficient with an additive amount of about 10 ppm to 20000 ppm.

[0056] Further, when the treatment load of the metal material to be treated on the treatment liquid of the present invention is high, it is preferable to add a chelating agent capable of chelating metal ions eluted by the etching reaction. Examples of chelating agents that can be used in the treatment liquid of the present invention include ethylenediamin tetraacetic acid (EDTA), darconic acid, heptogluconic acid, glycolic acid, thaenoic acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid. , Malic acid, salicylic acid, and salts of these chelating agents. The content of these chelating agents is not particularly limited, but a sufficient effect can be obtained with an additive amount of about 1 ppm to 10,000 ppm.

[0057] In addition, it is preferable to add a water-soluble polymer compound having an ionic reactive group in the molecule and Z or a water-dispersible polymer compound to the treatment liquid of the present invention. Examples of such compounds include polybutyl alcohol, poly (meth) acrylic acid, copolymers of acrylic acid and methacrylic acid, acrylic monomers such as ethylene and (meth) acrylic acid and (meth) acrylate. Copolymer with ethylene, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin, epoxy resin, polyamidoamine, polyamine, polyamine derivative, polyallylamine, polyallylamine derivative, polyamide Examples include amine derivatives, polyvinylamine, polybulamine derivatives, tannin and tannic acid and salts thereof, and phytic acid. There is no particular restriction on the concentration of the above compound added, but it is preferably about 1 ppm to 10,000 ppm, and such an added amount exhibits a sufficient effect.

[0058] In addition, at least one surfactant selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a force thione surfactant is added to the treatment liquid of the present invention. I prefer that. When a metal material is surface-treated using this surface treatment solution, a good film can be formed without degreasing the treated metal material in advance and cleaning it as described later. In other words, this surface treatment solution can be used as a degreasing chemical treatment surface treatment agent.

[0059] The treatment method of the present invention includes a treatment liquid contact step of bringing the treatment liquid of the present invention into contact with a metal material containing iron and Z or zinc, and the surface of the metal containing iron and / or zinc. It is a processing method.

[0060] In the surface treatment method of the present invention, it is only necessary to bring the treatment liquid of the present invention into contact with the metal material containing iron and Z or zinc. As a result, a film made of the oxide of element (A) and Z or hydroxide is deposited on the surface of the metal material, and a surface-treated film layer having excellent adhesion and corrosion resistance is formed.

For this contact treatment, various methods such as spray treatment, immersion treatment and pouring treatment can be used, and this contact method does not affect the performance.

It is chemically difficult to obtain a metal hydroxide contained in the coating film of component (A) as a pure hydroxide, and generally, a form in which hydrated water is attached to the metal oxide. Is also in the category of hydroxides. Therefore, the metal hydroxide is finally converted into an oxide by heating. The structure of the surface treatment film layer in the present invention is such that when it is dried at room temperature or low temperature after being subjected to surface treatment, it is in a state in which oxides and hydroxides are mixed, and when it is dried at high temperature after surface treatment, It is thought that there is only a lot of food or acid.

[0061] The metal material containing iron and Z or zinc is preferably cleaned by degreasing. The method of degreasing treatment is not particularly limited, and a conventionally known method can be used.

As described above, when the treatment liquid of the present invention contains the surfactant, the metal material containing iron and Z or zinc may be degreased in advance, cleaned, and removed. A good film can be formed. That is, in this case, the degreasing treatment and film conversion treatment of the metal material containing iron and Z or zinc are simultaneously performed in the treatment liquid contact step.

[0062] The conditions for using the treatment liquid of the present invention are not particularly limited.

The reactivity of the treatment liquid of the present invention is the ratio of Kl = BZA, which is the ratio of the total mass concentration B to the total mass concentration A, and K2 = CZA, which is the ratio of the total mass concentration C to the total mass concentration A. It can be freely controlled by changing.

Further, when at least one of the component (D) fluorine-containing compounds is used, it can be controlled by changing the free fluorine ion concentration D. Therefore processing temperature The degree and processing time can be changed to V, etc., in combination with the reactivity of the processing bath.

[0063] In the treatment method of the present invention, the metal material containing iron and / or zinc may be subjected to electrolytic treatment in the state of contact with the treatment liquid of the present invention.

In this case, a hydrogen reduction reaction occurs at the interface between the metal material containing iron and Z or zinc as the cathode, and the pH rises. As the pH rises, the stability of the compound containing the component (A) element at the cathode interface decreases, and the surface treatment film is deposited as an acid or water-containing hydroxide.

[0064] After the treatment liquid of the present invention is brought into contact with the metal material containing iron and Z or zinc, or after being subjected to electrolytic treatment, cobalt, nickel, tin, copper, titanium, and zirconium-umuka It can be contacted with an acidic aqueous solution containing at least one selected from the group consisting of these, or a treatment solution containing at least one of a water-soluble polymer compound and a water-dispersible polymer compound. Thereby, the effect of the present invention can be further enhanced.

[0065] The surface-treated film layer obtained by the present invention is a thin film and exhibits excellent coating performance. If the surface condition of the metal material to be treated is abnormal, there may be a minute defect in the surface treatment film layer. Accordingly, the acidic aqueous solution containing at least one selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium, or a water-soluble polymer compound and a water-dispersible polymer compound are selected. By contacting with a treatment solution containing at least one polymer compound, the defect is covered and the corrosion resistance is further enhanced.

[0066] Here, there is no particular limitation as to at least one source from which the group force consisting of cobalt, nickel, tin, copper, titanium, and zirconium is also selected, but it is easy to obtain the metal element. Oxides, hydroxides, fluorides, complex fluorides, chlorides, nitrates, oxynitrates, sulfates, oxysulfates, carbonates, oxycarbonates, phosphates, oxyphosphates, oxalates, An oxyshinonate, an organometallic compound, and the like can be used. In addition, it is preferable that the acidic aqueous solution containing the metal element has a pH of 2 to 6. Acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, and organic acids, sodium hydroxide, Potassium hydroxide, lithium hydroxide, alkali metal salts, ammonia, ammonia salts, amines, etc. It can be adjusted with Lucari.

[0067] Further, at least one polymer compound selected from the water-soluble polymer compound and the water-dispersible polymer compound may be, for example, polybulal alcohol, poly (meth) acrylic acid, acrylic acid and methacrylic acid. Copolymers with acids, copolymers of ethylene and acrylic monomers such as (meth) acrylic acid and (meth) acrylate, copolymers of ethylene and vinyl acetate

, Polyurethane, amino-modified phenolic resin, polyester resin, epoxy resin, polyamineamine, polyamine, polyamine derivative, polyallylamine, polyallylamine derivative, polyamidoamine derivative, polybulamine, polybulamine amine, tannin and tannic acid and its salts, and phytin An acid or the like can be used.

[0068] As described above in detail, the present invention provides an oxide layer of component (A) and a coating layer having Z or hydroxide strength on the surface of the metal material to be treated, or component (A). It is possible to drastically improve the corrosion resistance of metal materials by providing a coating layer that is a mixture of the above-mentioned coating layer and an oxide layer of the metal element of component (B) and a coating layer of Z or hydroxide. It is what. Here, the film made of the acid compound and Z or hydroxide compound of the component (A) has a chemically stable property and is hardly affected by acid or alkali.

[0069] Here, in a corrosive environment under an actual metal coating, the pH decreases in the anode portion where the metal elution occurs, and the pH increases in the force sword portion where the reduction reaction occurs. Therefore, a surface-treated film that is inferior in acid resistance and alkali resistance dissolves in a corrosive environment and loses its effect. In the present invention, the oxide (A) and Z or hydroxide films of the component (A) are difficult to be attacked by acid and alkali, and the present invention is a uniform surface treatment film on the surface of the metal to be treated. Therefore, the excellent effect is maintained even in a corrosive environment.

[0070] Further, the oxides and hydroxides of the metal elements contained in the film form a network structure through the metal and oxygen, so that they are very good noble films. Corrosion of metal materials varies depending on the environment in which it is used. Generally, it is oxygen demand type corrosion in the presence of water and oxygen, and the corrosion speed is accelerated by the presence of components such as chloride. Here, since the coating layer of the present invention has a barrier effect against water, oxygen and corrosion promoting components, it can exhibit excellent corrosion resistance. [0071] In addition to the component (A) and the component (B), the composition of the present invention and the treatment liquid of the present invention contain the component (C), and the quantitative ratio thereof is A specific range. For this reason, a chemical conversion reaction is accompanied when the surface treatment film is deposited. With the chemical reaction, the adhesion of the film becomes extremely high.

[0072] Here, in order to increase the corrosion resistance of ferrous metal materials such as cold-rolled steel sheets, hot-rolled steel sheets, pig iron and sintered materials using the barrier effect, the surface treatment film layer is attached. The amount is preferably 20 mg / m ² or more, more preferably 30 mg / m ² or more, more preferably 40 mg / m ² or more, in terms of element of component (A).

[0073] Further, in order to increase the corrosion resistance of zinc-based metal materials such as zinc, zinc-plated steel sheets, and electrogalvanized steel sheets, the amount of the surface treatment coating layer applied is 15 mg in terms of element of component (A). / m ² or more is preferable 20 mg / m ² or more is more preferable.

If the amount of adhesion is too small, the barrier effect cannot be exhibited sufficiently, and it becomes difficult to obtain excellent corrosion resistance.

[0074] Furthermore, there is no particular limitation on the upper limit of the adhesion amount of the iron-based metal material and the zinc-based metal material, but if the adhesion amount is too large, cracks are likely to occur in the surface treatment film layer, and a uniform film is formed. The work to obtain becomes difficult. Therefore, the adhesion amount of both iron-based material and zinc-based material is preferably lg / m ² or less, more preferably 800 mg / m ² or less, in terms of element of component (A).

Example

[0075] Examples are given below together with comparative examples to specifically explain the effects of the surface treatment liquid and the surface treatment method of the present invention. In addition, the to-be-treated material, the degreasing agent, and the paint used in the examples are arbitrarily selected from commercially available materials, and the actual use of the surface treatment liquid and the surface treatment method of the present invention. It is not intended to limit.

[0076] (Test plate)

The abbreviations and breakdown of the test plates used in the examples and comparative examples are shown below.

• SPC (Cold rolled steel sheet: JIS—G—3141)

• EG (electrogalvanized steel sheet: weight per unit area 20g / m ² )

[0077] (Processing step) In Examples 1 to 5 and Comparative Examples 1 to 3, surface treatment was performed in the following treatment steps.

Alkaline degreasing → Washing → Chemical conversion treatment → Washing → Pure water washing → Drying.

[0078] In Example 6, the surface treatment was performed in the following treatment steps.

Alkaline degreasing → Washing → Chemical conversion treatment → Washing → Post treatment → Pure water washing → Drying.

[0079] In Example 7, surface treatment was performed by the following treatment steps.

Alkaline degreasing → water washing → electrochemical conversion treatment → water washing → pure water washing → drying.

[0080] Further, Comparative Example 4 was processed in the following processing steps.

Alkaline degreasing → Washing → Surface conditioning → Zinc phosphate treatment → Washing → Pure water washing → Drying.

[0081] Alkaline degreasing was performed using 2% Fine Cleaner L4460A (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) and Fine Cleaner L4460B (registered trademark: manufactured by Nippon Paishiro Rising Co., Ltd.) in both Examples and Comparative Examples. 1. Dilute to 4% with tap water and spray on treated plate for 40 seconds at 40 ° C.

[0082] The washing with water and the washing with pure water after the film treatment were sprayed on the plate to be treated for 30 seconds at room temperature in both Examples and Comparative Examples.

The drying was performed by leaving it in a room temperature room.

[0083] <Example 1>

Using a zirconium sulfate aqueous solution, lanthanum sulfate, and nitric acid, a surface treatment composition having a total mass concentration ratio K1 = BZA = 0.1, and a total mass concentration ratio K2 = CZA = 0.01 was prepared. The surface treatment composition was diluted with ion-exchanged water so that the mass concentration of the elemental zirconium was 8000 ppm, and a surface treatment solution having a pH of 3.2 was prepared using sodium hydroxide. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 50 ° C. for 180 seconds for surface treatment.

Using a hexafluorozirconium aqueous solution, samarium nitrate and nitric acid, a surface treatment composition having a total mass concentration ratio K1 = BZA = 2.0 and a total mass concentration ratio K2 = CZA = 50 was prepared. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of the elemental zirconium is lOOppm, and the free fluorine ion concentration is 25 ppm using hydrofluoric acid and ammonia (Fluorine ion meter: Toa Denki Kogyo Co., Ltd.) Company IM-55G), pH is 3 A surface treatment solution of 6 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 45 ° C. for 150 seconds for surface treatment.

Preparation of surface treatment composition with total mass concentration ratio K1 = BZA = 5.0 and total mass concentration ratio K2 = CZA = 20 using zirconium nitrate aqueous solution, acid 匕 hafnium, acid 匕 gadolinium and potassium nitrate did. The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the zirconium element and hafnium elements is 50 ppm. To this solution, succinic acid is added at 100 ppm, and potassium fluoride is added. Then, a surface treatment solution having a free fluorine ion concentration of 20 ppm (fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH of 4.0 was prepared using lithium hydroxide. The test plate that had been degreased and washed with water was immersed in the above surface treatment solution heated to 60 ° C for 120 seconds to perform surface treatment o

[0086] <Example 4>

For surface treatment with total mass concentration ratio K1 = BZA = 35 and total mass concentration ratio K2 = C / A = 100 using zirconium nitrate aqueous solution, salt-lanthanum aqueous solution, acid erbium, sodium nitrate and sodium nitrate The composition was adjusted. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of zirconium element is 20 ppm, and the concentration of free fluorine ions is 15 ppm using hydrofluoric acid and calcium hydroxide (fluorine ion meter: Toa Denki Kogyo) IM-55G manufactured by Co., Ltd.), a surface treatment solution having a pH of 3.0 was prepared. The test plate that had been degreased and washed with water was subjected to surface treatment by spraying for 120 seconds with the above surface treatment solution heated to 55 ° C.

For surface treatment with total mass concentration ratio K1 = BZA = 0.4, total mass concentration ratio K2 = CZA = 8.0 using titanium nitrate aqueous solution, hexafluorosilicic acid aqueous solution, acid-sodium prasedium and nitric acid power lithium The composition was adjusted. The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the titanium element mass concentration and the silicon element mass concentration is 2500 ppm, and the free fluorine ion concentration is further increased by using ammonium fluoride and ammonia. Is 100 ppm (fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.), pH is 2.9 A surface treatment solution was prepared. The surface treatment was carried out by spraying the test plate that had been degreased and washed with water with the above surface treatment solution heated to 65 ° C for 300 seconds.

Surface treatment with total mass concentration ratio K1 = BZA = 1.0, total mass concentration ratio K2 = CZA = 0.5 using zirconium nitrate aqueous solution, hexafluorotitanium aqueous solution, lanthanum chloride and iron nitrate The composition for preparation was prepared. The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the zirconium element mass concentration and the titanium element mass concentration is 200 ppm. Furthermore, free fluorine is used using ammonium fluoride and potassium hydroxide hydroxide. A surface treatment solution having an ion concentration of 50 ppm (fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.) and pH of 4.2 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 60 ° C. for 200 seconds for surface treatment, and then washed with water and post-treated. The post-treatment liquid used at this time was an aqueous solution having a titanium mass concentration of 200 ppm and a nickel mass concentration of 50 ppm as a metal element using a hexafluorotitanium aqueous solution and nickel nitrate. After heating to ° C, a solution adjusted to pH 4.5 with sodium hydroxide was used.

Preparation of surface treatment composition with total mass concentration ratio K1 = BZA = 3.0 and total mass concentration ratio K2 = CZA = 3.0 using hexafluorozirconium aqueous solution, yttrium sulfate and nitric acid did. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of zirconium element is 200 ppm, and 50 ppm of EDTA is added to this solution, and further free fluoride ions are added using hydrofluoric acid and sodium hydroxide. A surface treatment solution having a concentration of 80 ppm (fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.) and pH of 2.8 was prepared. Using a test plate that had been degreased and washed with water as a cathode, and using a carbon electrode as the anode, surface treatment was performed by electrolysis for 10 seconds in the 5AZdm ² electrolysis condition in the above surface treatment solution at room temperature.

[0090] <Comparative Example 1>

Using a zirconium nitrate aqueous solution, holmium nitrate and nitric acid, a surface treatment composition having a total mass concentration ratio K1 = B / A = 0.01 and a total mass concentration ratio K2 = CZA = 10 was prepared. did. The surface treatment composition was diluted with ion-exchanged water so that the mass concentration of zirconium element was lOOppm, and a surface treatment solution having a pH of 3.0 was prepared using sodium hydroxide. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 55 ° C. for 180 seconds for surface treatment.

[0091] <Comparative Example 2>

Surface treatment composition with total mass concentration ratio K1 = BZA = 5.0, total mass concentration ratio K2 = CZA = 200, using hexafluorozirconium aqueous solution, acid citrus pium and sodium nitrate Adjusted. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of zirconium element is 4 ppm. Further, free fluoride ions are 20 ppm using potassium fluoride and potassium hydroxide (Fluorine ion meter: Toa Denki Kogyo Co., Ltd.) A surface treatment solution having a pH of 3.8 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 60 ° C. for 120 seconds for surface treatment.

[0092] <Comparative Example 3>

A surface treatment composition having a total mass concentration ratio K1 = BZA = 70 and a total mass concentration ratio K2 = CZA = 50 was prepared using an aqueous hexafluorotitanium solution, gallium sulfate, potassium nitrate, and ammonium nitrate. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of titanium element is 50 ppm, and further, the concentration of free fluorine ions is 400 ppm using ammonium fluoride and ammonia (fluorine ion meter: Toa A treatment liquid for surface treatment having a pH of 2.8 was prepared. The test plate that had been degreased and washed with water was subjected to surface treatment by spraying for 150 seconds with the above-mentioned surface treatment solution heated to 50 ° C.

[0093] <Comparative Example 4>

On a test plate that has been degreased and washed with water, prepare a solution prepared by diluting Preparen ZN (registered trademark: Nippon Parkerizing Co., Ltd.), a surface conditioning agent, to 0.1% with tap water at room temperature for 30 seconds. After spraying, Palbond L3020 (registered trademark: Nippon Parkerizing Co., Ltd.) was diluted to 4.8% with tap water, and after adding 200 ppm of sodium hydrogen fluoride reagent as fluorine, total acidity and free acidity Was immersed in a 43 ° C zinc phosphate phosphatization solution adjusted to the center of the catalog value to deposit a zinc phosphate coating. [0094] (Evaluation of surface treatment film and adhesion amount measurement)

The appearance of the test plate after the surface treatment of the examples and comparative examples was visually evaluated, and the amount of the surface treatment film layer deposited was measured using a fluorescent X-ray analyzer (System 3270; manufactured by Rigaku Denki Kogyo Co., Ltd.). Measured.

[0095] (Preparation of coating performance evaluation board)

In order to evaluate the coating performance of the surface-treated plates of Examples and Comparative Examples, coating was performed in the following steps. Cationic electrodeposition coating → pure water washing → baking → intermediate coating → baking → top coating → baking.

[0096] Cationic electrodeposition coating: Epoxy-based cationic electrodeposition coating (Electron 9400: manufactured by Kansai Paint Co., Ltd.), voltage 200V, film thickness 20 / ζ πι, 175 ° C 20 minutes baking

[0097] Intermediate coating: Aminoalkyd paint (Amirac TP—37 gray: manufactured by Kansai Paint Co., Ltd.)

), Spray coating, film thickness 35 μm, baking at 140 ° C for 20 minutes

[0098] Top coat: Aminoalkyd paint (Amirac TM-13 White: manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 / ζ πι, baking at 140 ° C for 20 minutes

[0099] (Coating performance evaluation)

The coating performance of the examples and comparative examples was evaluated according to JIS standards. The evaluation items are shown below. The coating film at the completion of electrodeposition coating is referred to as an electrodeposition coating film, and the coating film at the time of completion of top coating is referred to as a 3c _0ats coating film.

(0 Salt spray test: electrodeposition coating

(ii) Adhesion test: 3 _CO ats coating

[0100] (Salt spray test (SST test))

5% salt water was sprayed for 720 hours (according to JIS —Z—2371) on the electrodeposition coated plate with a crosscut cut with a sharp cutter. After spraying, the maximum swollen width on both sides from the crosscut part was measured and evaluated according to the following evaluation criteria.

5mm or more 7mm not yet ： O

8mm or more and less than 9mm: Δ 9mm or more: X

[0101] (Adhesion test (cross-cut method))

Using a sharp cutter on the 3coats coating film, 25 cuts were made in accordance with JIS-K-5600-5-6 by making 6 cuts in the vertical and horizontal directions at 2mm intervals. The grid area was peeled off with tape and evaluated by an evaluation method according to the JIS standard.

[0102] Tables 1 and 2 show the appearance evaluation results of the surface treatment films obtained in Examples and Comparative Examples, and the amount of adhesion of the surface treatment film. In the example, a uniform film could be obtained for both the SPC material and the EG material, and the target film adhesion amount could be obtained. On the other hand, in Comparative Example 1, since the total concentration ratio K1 was small, the SPC material and the EG material were both unable to deposit the surface treatment film. In Comparative Example 2, since the content of component (A) was small, both the SPC material and EG material were unable to deposit the surface treatment film. In Comparative Example 3, since the total mass concentration ratio K1 was large and the free fluorine ion concentration D was high, the SPC material and the EG material were both unable to deposit the surface treatment film. Since Comparative Example 4 was a conventional zinc phosphate treatment, it was possible to form a surface treatment film on both the SPC material and the EG material.

[0103] The coating performance evaluation results (salt spray test) of the electrodeposition coating film are shown in Table 3. In the examples, both SPC material and EG material showed good corrosion resistance. On the other hand, in Comparative Example 1, since the total concentrated mass ratio K1 was small and K1 was small, the film (A) was not sufficiently effective in promoting the film formation by the component (B). As a result, both the SPC and EG materials did not deposit a lot of surface treatment film, and the corrosion resistance was poor. In Comparative Example 2, since the content of component (A) was small, the target film adhesion amount could not be obtained for both SPC and EG materials, and the corrosion resistance was poor. In Comparative Example 3, since the total mass concentration ratio K1 is large and K1 is high and the free fluorine ion concentration D is high, the targeted coating amount cannot be obtained for both the SPC material and the EG material, and the corrosion resistance is poor. Comparative Example 4 is a zinc phosphate treatment that is currently commonly used as a base for cationic electrodeposition coating. The examples showed excellent coating performance at all levels compared to Comparative Example 4! /.

[0104] Table 4 shows the evaluation results of the adhesion of the 3c _0a ts plate. The examples showed good adhesion to all the test plates. As for the comparative examples, the level showing good adhesion to the test plate was strong in all the comparative examples except Comparative Example 4 as well as the corrosion resistance of the electrodeposition coated plate. [0105] From the above results, the surface treatment film having excellent adhesion and corrosion resistance is obtained by using the surface treatment composition, the surface treatment solution, the surface treatment method, and the surface treatment metal material which are the products of the present invention. It is clear that can be deposited.

[0106] [Table 1]

[0107] [Table 2]

Total amount of component (A) (mg / in ² )

SPC EG

Example 1 60 41 Male example 2 100 78 Difficult example 3 65 41 Example 4 20 16 Male example 5 45 32 Male example 6 90 75 Difficult example 7 50 42 Comparison 1 6 3 Comparison 2 4 2 Comparison 3 5 3 Hiei 4 2.0 (g / m ² )

※ Ri

Board SST 纖 result

SPC EG

Male Example 1 © Yes Male Example 2 © Yes Example 3 ◎ ○ Example 4 ◎ ○ Example 5 © 〇 Example 6 ◎ 〇 Example 7 ◎ 〇 Comparison 1 XX Comparison 2 XX Comparison 3 XX Comparison 4 © 〇

Adhesiveness (Cross cut bowl method) * Evaluation conforms to JIS-K-5600-5-6

SPC EG

Male example 1 0 0 Difficult example 2 0 0 Difficult example 3 0 0 Difficult example 4 0 0 Male example 5 0 0 Example 6 0 0 Example 7 0 0 Comparison 1 2 1 Comparison 2 2 2 Comparison 3 2 2 Ratio shelf 4 0 0

Claims

The scope of the claims

[1] Next component (A), component (B), and component (C):

(B) Compounds containing Y and Z or lanthanoid elements

(C) Nitric acid and Z or nitrate compounds

Containing

The ratio of the total mass concentration B of the Y and Z or lanthanoid elements in the component (B) to the total mass concentration A of the elements in the component (A) K1 = BZA force 0.05 ≤ K 1 ≤ 50 And

Total quality in terms of NO of nitrogen atoms in component (C) relative to total mass concentration Α

Three

The ratio of quantity concentration C is K2 = CZA force 0.01≤K2≤200,

[2] In addition, the following component (D):

(D) At least one fluorine-containing compound

The composition for surface treatment according to claim 1, comprising:

[3] Next ingredient (Α), ingredient (Β), and ingredient (C):

(B) Compounds containing Y and Z or lanthanoid elements

(C) Nitric acid and Z or nitrate compounds

Containing

Three

The ratio of quantity concentration C is K2 = C / A, 0.01 ≤ K2 ≤ 200,

The total mass concentration Α is 10ppm≤A≤lOOOOppm,

Treatment liquid for surface treatment of metals containing iron and Z or zinc.

[4] Furthermore, the following component (D): (D) At least one fluorine-containing compound

The treatment liquid for surface treatment according to claim 3, wherein the free fluorine ion concentration D is 0.001ppm≤D≤300ppm.

[5] The surface treatment solution according to claim 3 or 4, wherein the pH is 6.0 or less.

[6] Furthermore, HC1, HSO, HC10, HBrO, HNO, HMnO, HVO, H2O, HWO, HMo

2 4 3 3 2 4 3 2 2 2 4 2

Contains 10 to 20000 ppm of at least one selected from the group consisting of O and salts thereof

Four

The treatment liquid for surface treatment according to any one of claims 3 to 5.

[7] Further, ethylenediamine amine acetic acid, darconic acid, heptogluconic acid, dalcholic acid, thaenoic acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid

The surface treatment treatment solution according to any one of claims 3 to 6, comprising 1 to LOOOOppm of at least one selected from the group force consisting of salt power.

[8] The treatment liquid for surface treatment according to any one of [3] to [7], further comprising a water-soluble polymer compound and Z or a water-dispersible polymer compound.

[9] The treatment for surface treatment according to any one of [3] to [8], further comprising at least one selected from nonionic surfactants, anionic surfactants and cationic surfactants. liquid.

[10] A metal containing iron and / or zinc having a treatment liquid contact step of contacting the surface treatment liquid according to any one of claims 3 to 8 with a metal material containing iron and Z or zinc. Surface treatment method.

[11] A treatment liquid contact step of bringing the metal material containing iron and Z or zinc into contact with the treatment liquid for surface treatment according to claim 9 and simultaneously performing a degreasing treatment and a film forming treatment on the metal material. Surface treatment method of metal containing iron, Z and zinc.

12. The surface treatment method according to claim 10 or 11, wherein the metal material containing iron and Z or zinc is a metal material cleaned by a degreasing treatment.

13. The surface treatment method according to any one of claims 10 to 12, wherein in the treatment liquid contact step, the metal material containing iron and Z or zinc is used as a cathode.

[14] Furthermore, after the treatment liquid contact step,

In the metal material containing iron and Z or zinc, cobalt, nickel, tin, copper, titanium 14. The surface treatment method according to claim 10, further comprising a step of contacting an aqueous solution containing at least one selected from the group consisting of a zirconium and a zirconium catalyst.

[15] Furthermore, after the treatment liquid contact step,

The surface treatment according to claim 10, further comprising a step of bringing the metal material containing iron and Z or zinc into contact with an aqueous solution containing a water-soluble polymer compound and Z or a water-dispersible polymer compound. Method.

[16] The surface of the metal material containing iron, which is formed by the surface treatment method according to any one of claims 10 to 15, contains the element of the component (A), and adheres in terms of the element A metal material containing iron having a surface-treated coating layer having an amount of 20 mg / m ² or more.

[17] The element containing the element (A) formed by the surface treatment method according to any one of claims 10 to 15 on the surface of the metal material containing zinc, and the element-converted attachment A metal material containing zinc having a surface-treated coating layer having an amount of 15 mg / m ² or more.